CN106422965A - Synthetic method of chitosan surface active agent for improving morphology and dispersibility of ferroferric oxide - Google Patents

Synthetic method of chitosan surface active agent for improving morphology and dispersibility of ferroferric oxide Download PDF

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Publication number
CN106422965A
CN106422965A CN201610826004.4A CN201610826004A CN106422965A CN 106422965 A CN106422965 A CN 106422965A CN 201610826004 A CN201610826004 A CN 201610826004A CN 106422965 A CN106422965 A CN 106422965A
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synthetic method
shitosan
sodium
active agent
surface active
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罗情丹
毕彩丰
范玉华
赵宇
张笑银
万霖
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Ocean University of China
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Ocean University of China
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to a synthetic method of a chitosan surface active agent for improving morphology and dispersibility of ferroferric oxide. The synthetic method comprises the steps of preparing 2-hydroxy-3-chloro propanesulfate by using sodium sulfite, sodium hydrogen sulfite and epoxy chloropropane, wherein the molar ration of the sodium sulfite to the sodium hydrogen sulfite and to the epoxy chloropropane is (0.1-0.5) : (0.5-1.0) : (0.3-0.8); adding the 2-hydroxy-3-chloro propanesulfate and sodium hydroxide into distilled water, raising the temperature of the mixture, conducting epoxidation reaction, then adding chitosan which is subjected to swelling by 40% sodium hydroxide, repeated freezing and unfreezing, heating and stirring the mixture to obtain water soluble chitosan sulphonate surface active agent. The chintosan surface active agent can improve the morphology of the ferroferric oxide remarkably, make the morphology of ferroferric oxide granule present globose and improve the dispersibility of the ferroferric oxide. The raw materials of the product are easy to obtain, are natural and non-toxic, and can eliminate environmental pollution and achieve circular economy. The chitosan surface active agent is low in cost and easy to operate.

Description

A kind of conjunction of the shitosan surfactant for improving ferroso-ferric oxide pattern and dispersibility Become method
Technical field
The present invention relates to a kind of surfactant and its synthetic method, and in particular to a kind of shitosan sulphonate surfactant Agent and its synthetic method.
Background technology
Shitosan derives from the ocean such as Crusta Penaeus seu Panulirus, Carapax Eriocheir sinensis solid waste, using these discarded shrimp and crab shells as raw material production Shitosan, both turned waste into wealth, and had purified environment again, killed two birds with one stone.Used as a kind of nontoxic natural materials, shitosan has a lot Superior characteristic, such as good biocompatibility and biological degradability, hygroscopicity, biocidal property, film property, adsorptivity etc..But shell The water insoluble and organic solvent of polysaccharide, is only capable of being dissolved in acidic aqueous solution, which greatly limits the application of shitosan.
The focus of at present novel surfactant research concentrates on that prepare from natural product can be with biodegradable table Face activating agent.Shitosan surfactant had not only remained the advantage of shitosan but also had shown the property of surfactant, and shell is gathered Sugar and surfactant combine its unique structural behaviour advantage, extensive application prospect.
Shitosan cationic surfactant and the research of shitosan amphoteric surfactant are more, but shitosan anion table Face activating agent relevant report is less.
Ferroso-ferric oxide（Fe3O4）It is the main original of the magnetic toner in the electrostatic development equipment such as printer, photocopier Material, for producing the Fe of magnetic toner3O4To its granule-morphology, size and distribution, magnetic data, surface characteristic, stability Deng all there is strict demand.
Current powdered ink Fe3O4Synthesis be typically all adopt FeSO4For raw material, obtain through precipitation oxidation, working condition is not With, it is possible to obtain the product of different-shape and different magnetic datas, wherein grain diameter, specific surface area, satisfy magnetic, remanent magnetism, coercive Its use of the impact such as power, dispersibility, stability.Due to nanometer Fe3O4Magnetic particle has larger specific surface area and dipole is mutual Active force, the surface energy of particle is of a relatively high and itself has magnetic again, therefore nanometer Fe3O4Particle is often in the form of aggregate There is the gross energy so as to reduce system, therefore its dispersibility is also poor.The surfactant being suitable for is added to powdered ink level Fe3O4 Synthesis just seem extremely important.At present, surfactant and shitosan each individually study very many, but can be notable Improve Fe3O4The research of the shitosan surfactant of pattern and dispersibility is also little.
Content of the invention
For the problems referred to above, it is an object of the invention to provide one kind is with shitosan as raw material, Fe is significantly improved3O4Pattern and The surfactant of dispersibility and its synthetic method.
The present invention synthesizes shitosan anion surfactant with shitosan as raw material using N- alkylated reaction.Its knot Structure and synthetic route are as follows：
Wherein, shitosan is the chitin that deacetylation is 95%, and its viscosity-average molecular weight is 1.91 × 105.
The synthetic method of shitosan surfactant of the present invention, comprises the steps：
（1）In distilled water, addition sodium sulfite, sodium sulfite, heating for dissolving, are slowly dropped into epoxychloropropane, stirring reaction For a period of time, ice bath cooling, is recrystallized to give 2- hydroxyl -3- chlorine propanesulfonate；
（2）2- hydroxyl -3- chlorine propanesulfonate and sodium hydroxide are added in distilled water, after rising warming the meridian epoxidation reaction, at addition Shitosan after reason, heated and stirred obtains shitosan sulfosalt surfactant.
The mol ratio of the sodium sulfite, sodium sulfite and epoxychloropropane is：（0.1～0.5）：（0.5～1.0）： （0.3～0.8）.
The step（1）In heating and temperature control at 10 DEG C～60 DEG C.
The step（1）The revolution of middle stirring is 300rpm～700rpm, and the time is 1h～3h.
The step（1）Middle recrystallization solvent for use is 1 for volume ratio:1 water and the mixed solvent of ethanol.
The step（2）Middle 2- hydroxyl -3- chlorine propanesulfonate, sodium hydroxide and shitosan addition are respectively（0.1mol ～0.4mol）、（0.1mol～0.5mol）、（1g～3g）.
The deacetylating degree of chitosan is 95%, and viscosity-average molecular weight is 1.91 × 105.
The step（2）The processing method of middle shitosan be with 40%NaOH swelling after, then repeatedly freezing, thaw.
The step（2）Middle temperature reaction temperature is 20 DEG C～70 DEG C, response time 2h～6h.
The step（2）Middle heating-up temperature be 50 DEG C～150 DEG C, stir speed (S.S.) 200rpm～500rpm, the time be 10h～ 20h.
Water-soluble chitosan surfactant obtained by above-mentioned synthetic method is pale yellow powder shape solid.Viscous with Ubbelohde Degree has counted using progressively Dilution the viscosity-average molecular weight of product,M= 1.28 × 105, product is measured using maximum bubble method The CMC value of thing is 2.50 × 10-7mol·L-1, surface tension is 48 mN m-1.
Advantages of the present invention is easy to get for products material, Nantural non-toxic, eliminate environmental pollution and realize recycling economy, small investment, Easy to operate.For change Fe3O4Pattern has good effect so that Fe3O4Grain shape is closer to spherical, and dispersibility is more preferable.
Description of the drawings
Fig. 1 is the infrared spectrogram of the shitosan surfactant obtained by embodiment 1.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the shitosan surfactant obtained by embodiment 1.
Fig. 3 is the Fe that non-shell adding polysaccharide surfactant is obtained3O4Electron microscope.
Fig. 4 is the Fe for adding 1wt% shitosan surfactant to obtain3O4Electron microscope.
Specific embodiment
The present invention is described in detail below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1：
（1）0.2mol Na is added in there-necked flask2SO3、0.62 mol NaHSO3, heat and be dissolved in distilled water, then slowly 0.54 mol epoxychloropropane of Deca, temperature control is stirred vigorously 2 h at 30 °C or so under 600rpm, ice bath is cooled down, and is obtained white Color is crystallized, and reduce pressure sucking filtration, and filter cake is dried；Then volume ratio 1 is used:1 water and alcohol mixed solvent repeated recrystallize, obtain 2- hydroxyl Base -3- chlorine propanesulfonate.
（2）0.2 mol 2- hydroxyl -3- chlorine propanesulfonate and 0.24 mol NaOH is weighed, and 500 is dissolved in distilled water In mL there-necked flask, under 50 °C, react 4 h, be then charged with 2 g 40%NaOH swelling after, then repeatedly freeze and thaw The shitosan for processing, 90 °C of 16 h of stirring；Decompression sucking filtration, filtrate ethanol precipitation, then washing with acetone is used, be vacuum dried, Obtain pale yellow powder shape solid.
The infrared spectrogram of the shitosan surfactant synthesized by said method is shown in Fig. 1, and hydrogen nuclear magnetic resonance spectrogram is shown in figure 2.As in chitosan molecule chain, existing hydroxyl has amino again, acylation reaction both can occur on hydroxyl to generate ester, also can be in ammonia Occur on base to generate amide.The amino of shitosan is one-level amino, has lone pair electrons, with very strong nucleophilicity, can occur Many reactions, N- alkylation is that N- is acylated later another kind of critically important reaction.The saccharide residue of shitosan has two kinds of hydroxyls, and one It is C to plant6- OH, this is primary OH；Another kind is C3- OH, this is secondary hydroxyl groups.C6- OH is primary OH, in space conformation For upper, rotation can be relatively free to again, sterically hindered also little, and C3- OH is secondary hydroxyl groups, it is impossible to rotate freely, steric hindrance Also larger, so generally, C6The reactivity ratio C of-OH3- OH is big.On the other hand, amino activity is again than primary OH Activity larger.But which functional group is acylation reaction occur in actually, also with reaction dissolvent, the structure of acylating reagent, urge The factors such as agent, reaction temperature are closely related.
It is seen from figure 1 that, shitosan surfactant is in 3419cm-1There is big and sharp absworption peak at place, and this peak is for O-H's The stretching vibration absworption peak multi-absorption peak Chong Die with the stretching vibration absworption peak of N-H, 1045cm-1Locate as C6The spy of-OH Property absworption peak, illustrates that the amino of only chitosan molecule there occurs alkylated reaction；1191cm-1And 1046cm-1There is absorption at place, says Sulfonic acid group is introduced in bright shitosan surfactant, it was demonstrated that 2- hydroxyl -3- chlorine propanesulfonate there occurs N- alkane with shitosan Glycosylation reaction.As can be seen from Figure 2, maximum displacement signal δ=4.652 ppm is the signal of proton on OH in product molecule structure；- CH2-（h）Doublet be hidden between δ=3.0-4.5 ppm in the signal of complicated multiplet；The proton for being combined with nitrogen-atoms （g）Chemical shift is more sensitive to condition determination, and in non-polar solven, after dilution, molecular link hydrogen bond disappears；When in a solvent When adding heavy water, as amino hydrogen atom is exchanged with heavy hydrogen, Absorption Line just disappears, and can confirm depositing for amino core using this point , the product for synthesizing in summary be.
Embodiment 2：
（1）0.15mol Na is added in there-necked flask2SO3、0.62 mol NaHSO3, heat and be dissolved in distilled water, Ran Houhuan Slow 0.49 mol epoxychloropropane of Deca, temperature control is stirred vigorously 2 h at 30 °C or so under 600rpm, ice bath is cooled down, and is obtained White crystals, reduce pressure sucking filtration, and filter cake is dried；Then volume ratio 1 is used:1 water and alcohol mixed solvent repeated recrystallize, obtain 2- hydroxyl Base -3- chlorine propanesulfonate.
（2）0.3 mol 2- hydroxyl -3- chlorine propanesulfonate and 0.24 mol NaOH is weighed, and 500 is dissolved in distilled water In mL there-necked flask, under 50 °C, react 4 h, be then charged with 2 g 40%NaOH swelling after, then repeatedly freeze and thaw The shitosan for processing, 80 °C of 13 h of stirring；Decompression sucking filtration, filtrate ethanol precipitation, then washing with acetone is used, be vacuum dried, Obtain pale yellow powder shape solid.
Contrast on effect example 1：
Take 250.0 ml FeSO4Solution（1.0 mol·L-1）, it is placed in 1000 ml there-necked flasks, adds 133.0 ml distillation Water, under nitrogen protection, carries out heating in water bath and is warmed up to 60 DEG C, under stirring, by the 4.25 mol L of 117.0 ml-1NaOH Solution（nNaOH：nFeSO4= 2:1）, uniformly it is added drop-wise in solution, after completion of dropping, stirring 10min, system pH 10.35, Milky Fe (OH) is now obtained2Suspension, is warmed up to 85 DEG C, and nitrogen is converted into air, maintains the ventilation of 50 ml/min Speed, after ventilation milky Fe (OH)2Suspension gradually becomes blackish green, then is changed into black, and system viscosity reduction is relatively delayed Slowly, Fe in system after reaction 6h30min3+：Fe2+Ratio reaches 2.0, stops blowing air.Oxidation reaction is cleaned multiple times with distilled water Product is vacuum dried 12h to sulfate radical-free ion, at 80 DEG C, is ground with mortar, sieves（500 mesh）, sealing preserve is standby.Sample TEM figure is shown in Fig. 3, as seen from Figure 3 when in reaction system additive-free when, nanometer Fe3O4Easily reunite between granule, cause to produce Product pattern heterogeneity, dispersive property is bad.
Effect example 1：
Take 250.0 ml FeSO4Solution（1.0 mol·L-1）, it is placed in 1000 ml there-necked flasks, adds 133.0 ml distillation Water, under nitrogen protection, carries out heating in water bath and is warmed up to 60 DEG C, under stirring, by the 4.25 mol L of 117.0 ml-1NaOH Solution（nNaOH：nFeSO4= 2:1）, uniformly it is added drop-wise in solution, after completion of dropping, stirring 10min, system pH 10.37, Milky Fe (OH) is now obtained2Suspension, adds shitosan sulfosalt surfactant 0.2g, reaction after being warmed up to 85 DEG C System has a small amount of bubble to produce, and nitrogen is converted into air, maintains the Ventilation Rate of 50 ml/min, milky Fe after ventilation (OH)2Suspension is changed into rapidly grey black, then is changed into black, and system viscosity reduces comparatively fast, after reaction 3h30min in system Fe3+：Fe2+Ratio reaches 2.0, stops blowing air.Oxidation reaction product is cleaned multiple times to sulfate radical-free ion with distilled water, 80 12h is vacuum dried at DEG C, is ground with mortar, is sieved（500 mesh）, sealing preserve is standby.Sample TEM figure is shown in Fig. 4, permissible by Fig. 4 Find out when 1.03% shitosan sulfosalt surfactant is added in reaction system, nanometer Fe3O4Pattern substantially changed Kind, pattern is spherical in shape, and dispersibility is improved, soilless sticking phenomenon.

Claims (10)

1. a kind of synthetic method of the shitosan surfactant for improving ferroso-ferric oxide pattern and dispersibility, walks including following Suddenly：
（1）Sodium sulfite and sodium sulfite, heating for dissolving are added in distilled water, epoxychloropropane is slowly dropped into, stirring is anti- Should for a period of time, ice bath is cooled down, and is recrystallized to give 2- hydroxyl -3- chlorine propanesulfonate；
（2）2- hydroxyl -3- chlorine propanesulfonate and sodium hydroxide are added in distilled water, after rising warming the meridian epoxidation reaction, add warp 40%NaOH is swelling, repeatedly freezing, thaw after shitosan, heated and stirred obtains water-soluble chitosan sulfosalt surfactant.
2. synthetic method according to claim 1, it is characterised in that：The step（1）Sulfite sodium, sodium sulfite Mol ratio with epoxychloropropane is：（0.1～0.5）：（0.5～1.0）：（0.3～0.8）.
3. synthetic method according to claim 1, it is characterised in that：The step（1）Middle heating and temperature control is at 10 DEG C ～60 DEG C.
4. synthetic method according to claim 1, it is characterised in that：The step（1）The revolution of middle stirring is 300rpm ～700rpm, the time is 1h～3h.
5. synthetic method according to claim 1, it is characterised in that：The step（1）Middle recrystallization solvent for use volume Than for 1:1 water and the mixed solvent of ethanol.
6. synthetic method according to claim 1, it is characterised in that：The step（2）Middle 2- hydroxyl -3- chlorine propane sulfonic acid Sodium, sodium hydroxide and shitosan addition are respectively（0.1mol～0.4mol）、（0.1mol～0.5mol）、（1g～3g）.
7. the synthetic method according to claim 1 or 6, it is characterised in that：The deacetylating degree of chitosan is 95%, and which glues Average molecular weight is 1.91 × 105.
8. synthetic method according to claim 1, it is characterised in that：The step（2）Middle temperature reaction temperature is 20 DEG C ～70 DEG C, response time 2h～6h.
9. synthetic method according to claim 1, it is characterised in that：The step（2）Middle heating-up temperature is 50 DEG C～150 DEG C, stir speed (S.S.) 200rpm～500rpm, the time is 10h～20h.
10. the shitosan surfactant that synthetic method according to any one of claim 1-9 is obtained.
CN201610826004.4A 2016-09-14 2016-09-14 Synthetic method of chitosan surface active agent for improving morphology and dispersibility of ferroferric oxide Pending CN106422965A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106904867A (en) * 2017-04-20 2017-06-30 福建清源科技有限公司 Concrete synergist containing chitosan sodium sulfonate and preparation method thereof
CN109385681A (en) * 2018-09-27 2019-02-26 浙江和也健康科技有限公司 A kind of broad-spectrum antiseptic healthcare function fiber and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0280051A (en) * 1988-09-15 1990-03-20 Ipposha Oil Ind Co Ltd Sterilizing and deodorizing high molecule
CN1651129A (en) * 2004-11-30 2005-08-10 中国日用化学工业研究院 Surface active agent alcohol ether glucoside and its preparation method
CN1844163A (en) * 2006-05-08 2006-10-11 武汉中唐生化科技有限公司 Process for preparing non-derivative biochemical water-soluble chitosan
CN104130339A (en) * 2014-07-31 2014-11-05 赵东育 Chemical synthetic method for hydroxypropyl chitin
CN105367687A (en) * 2015-12-09 2016-03-02 上海大学 Chitosan amphiphilic polymer surfactant, and synthetic method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0280051A (en) * 1988-09-15 1990-03-20 Ipposha Oil Ind Co Ltd Sterilizing and deodorizing high molecule
CN1651129A (en) * 2004-11-30 2005-08-10 中国日用化学工业研究院 Surface active agent alcohol ether glucoside and its preparation method
CN1844163A (en) * 2006-05-08 2006-10-11 武汉中唐生化科技有限公司 Process for preparing non-derivative biochemical water-soluble chitosan
CN104130339A (en) * 2014-07-31 2014-11-05 赵东育 Chemical synthetic method for hydroxypropyl chitin
CN105367687A (en) * 2015-12-09 2016-03-02 上海大学 Chitosan amphiphilic polymer surfactant, and synthetic method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
申云霞等: "壳聚糖磺酸盐表面活性剂的合成、表征及表面性能研究", 《中国海洋大学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106904867A (en) * 2017-04-20 2017-06-30 福建清源科技有限公司 Concrete synergist containing chitosan sodium sulfonate and preparation method thereof
CN106904867B (en) * 2017-04-20 2019-03-08 福建清源科技有限公司 Concrete synergist containing chitosan sodium sulfonate and preparation method thereof
CN109385681A (en) * 2018-09-27 2019-02-26 浙江和也健康科技有限公司 A kind of broad-spectrum antiseptic healthcare function fiber and preparation method thereof

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